Refreshing wafers having low-k dielectric materials

ABSTRACT

A low-k dielectric layer having a composition of silicon, oxygen and carbon is removed from a wafer. The low-k dielectric layer is removed by exposing a surface of the low-k dielectric layer to an oxygen-containing gas to oxidized the surface. The oxidized surface is immersed in an etching solution having HF and H 2 SO 4  to etch the low-k dielectric layer. The etched surface is exposed to at least one of (i) an etching solution having H 2 SO 4  and H 2 O 2 , and (ii) an RF or microwave energized oxygen-containing gas, to remove the low-k dielectric layer from the wafer.

BACKGROUND

Embodiments of the present invention relate to the refreshing of wafershaving low-k dielectric materials.

In the processing of substrates, such as semiconducting wafers anddisplays, a test wafer is often used to determine processing uniformity.During processing, a substrate is placed in a process chamber andsuitable processing conditions are maintained in the chamber. Processingof the substrate can involve, for example, energizing a process gas toetch the substrate or deposit material on the substrate. The substratesare typically processed in a series of processing steps to form a finalsubstrate product, which may be an integrated circuit having metalinterconnect metal layers with dielectric material in between. Toevaluate the results from one or more of the processing steps, a testwafer can be processed in the chamber in place of the productionsubstrate. The test wafer can be processed to determine processingresults such as the deposited film thickness uniformity and particlecounts, and the process parameters can be modified according to the testresults to provide improved processing performance. For example, for adeposition process, the test wafer may be processed to determine athickness uniformity, composition and wafer stress of a deposited film.

In one testing method, test wafers are used to evaluate processing of alow-k dielectric material on a substrate. Low-k dielectric materialshave a dielectric constant ‘k” that is lower than conventionaldielectric materials, such as silicon oxide, and may typically have a‘k’ value of less than about 3. Examples of low-k dielectric materialscan comprise compositions of silicon, oxygen and carbon, and evenhydrogen, such as for example, the “Black Diamond™” dielectric material,and such materials may be formed by a chemical vapor deposition method.Low-k dielectric layers can reduce an RC delay time in an integratedcircuit, allowing corresponding increases in metal interconnect density.Accordingly, the formation of low-k dielectric layers having propertiesthat meet the processing specification is important for the fabricationof high-density circuits, especially for circuits having feature sizesof less than about 100 nm.

After testing, the wafers used to evaluate low-k dielectric layerdeposition processes can be refreshed, by removing the low-k layer andrefurbishing the test wafer for subsequent process evaluations.Refreshing and reclamation of test wafers is desirable to cut down onthe cost of providing fresh test wafer materials. Refreshing may also bea suitable method of reusing production wafers with low-k dielectriclayers that were poorly processed. In one version, a wafer having alow-k dielectric layer is reclaimed by mechanically grinding the low-kdielectric material off the wafer, for example with a grinding wheel. Inanother version, a chemical solution is used to remove the material.

However, standard refreshing techniques often fail to suitably removelow-k dielectric materials. For instance, some low-k dielectricmaterials are difficult to remove chemically, as the combination oforganic and inorganic elements renders the material less reactive withmany chemical compositions, and many chemical compositions can convertthe low-k dielectric material into a gummy residue on the wafer. Also,conventional means such as grinding can excessively scratch andotherwise damage the wafer surface. Surface damage can undesirablyaffect the deposition of a low-k dielectric layer on the surface, andalter the deposition testing results. As such, conventionally reclaimedwafers are often only suitable as mechanical-grade testing wafers, forexample, for mechanical robot testing to evaluate wafer positioning, butmay not be suitable as test-grade wafers for evaluating substrateprocesses. The conventional refreshing methods may also erode away anexcessive amount of the wafer during the low-k removal process. Thisexcessive erosion can limit the number of times the wafer can bereclaimed for re-use, before disposal of the wafer becomes necessary.Accordingly, conventional refreshing techniques do not always providesatisfactory removal of low-k dielectric materials to allow re-use ofthe wafers.

Thus, it is desirable to be able to reclaim a wafer having a low-kdielectric material. It is furthermore desirable to be able to refresh atest wafer to remove a low-k dielectric layer, to provide a fresh testwafer for testing low-k dielectric layer deposition processes. It isfurther desirable to completely remove residual low-k dielectricmaterial from the test wafer in the refreshing process.

SUMMARY

In one version, a low-k dielectric layer having a composition ofsilicon, oxygen and carbon is removed from a wafer. The low-k dielectriclayer has a dielectric constant value ‘k’ of less than about 3. Thelow-k dielectric layer is removed by exposing a surface of the low-kdielectric layer to an oxygen-containing gas to oxidize the surface. Theoxidized surface is immersed in an etching solution having HF and H₂SO₄to etch the low-k dielectric layer. The etched surface is exposed to atleast one of (i) an etching solution having H₂SO₄ and H₂O₂, and (ii) anRF or microwave energized oxygen-containing gas, to remove the low-kdielectric layer from the wafer.

In another method of removing the low-k dielectric layer from the wafer,a fine grinding step is performed to grind the low-k dielectric layerwith a grinding surface having bonded particles of abrasive materialhaving a size of from about 1 micrometer to about 6 micrometers. Thewafer is polished after the fine grinding process.

In yet another method of removing the low-k dielectric layer, a grindingstep is performed to remove at least a portion of the low-k dielectriclayer. A chemical mechanical polishing step is performed by rotating thesurface of the wafer against a polishing pad having a hardness of atleast about 40, and applying a polishing slurry between the wafer andpolishing pad.

In still another method of removing the low-k dielectric layer, thesurface of the low-k dielectric layer is immersed in a first etchingsolution having a first composition that is selected to break Si—O bondsin the dielectric layer. The surface is also immersed in a secondetching solution having a second composition that is selected to breakSi—C bonds in the low-k dielectric layer. The low-k dielectric layer maybe substantially entirely removed from the wafer by the first and secondcleaning solutions.

In a further version, a method of refurbishing a wafer having a low-kdielectric layer with a composition of silicon, oxygen and carbon, andhaving a k value of less than about 3, is provided. The method involvesproviding a removable layer on the wafer and forming the low-kdielectric layer over the removable layer. The removable layer is etchedfrom the wafer by at least partially immersing the wafer in an etchingsolution, thereby removing the overlying low-k dielectric layer from thewafer.

DRAWINGS

These features, aspects and advantages of the present invention willbecome better understood with regard to the following description,appended claims, and accompanying drawings, which illustrate examples ofthe invention. However, it is to be understood that each of the featurescan be used in the invention in general, not merely in the context ofthe particular drawings, and the invention includes any combination ofthese features, where:

FIG. 1A is a partial sectional side view of an embodiment of a waferhaving a low-k dielectric material thereon;

FIG. 1B is a partial sectional side view of the wafer of FIG. 1A after acleaning process to remove the low-k dielectric material;

FIG. 2A is a partial top view of an embodiment of a fine grindingapparatus;

FIG. 2B is a partial sectional side view of the fine grinding apparatusof FIG. 2A;

FIG. 3 is a partial sectional side view of an embodiment of a polishingpad and wafer;

FIG. 4 is a partial sectional side view of an embodiment of a waferhaving a low-k dielectric layer over a removable layer; and

FIG. 5 is a partial sectional side view of an embodiment of a processchamber.

DESCRIPTION

A cleaning process can be performed to remove a low-k dielectric layer22 from a wafer 104, for example to allow the wafer 104 to be refreshedfor re-use as a test wafer, or to allow re-processing of the wafer. Thelow-k dielectric layer 22 comprises a low-k dielectric material having acomposition of carbon, silicon and oxygen, such as carbon-doped siliconoxide, and may even comprise an organosilicate glass (OSG). The low-kdielectric layer 22 may comprise a dielectric constant ‘k’ of less thanabout 3, such as from about 2.5 to about 2.8, and even less than about2.4. The low-k dielectric layer 22 may be formed by a deposition processsuch as a chemical vapor deposition process or a spin-on process.Examples of low-k dielectric materials include “BLACK DIAMOND™” and“SILK™” materials. The low-k dielectric layer 22 may be formed on anunderlying surface 26 of a wafer base 24, which may be, for example, asilicon wafer base, and may even substantially entirely cover theunderlying surface 26 of the wafer base 24, as shown in FIG. 1 a. Thelow-k dielectric layer 22 may comprise a substantially planar film (asshown) or may alternatively comprise a layer 22 having a plurality ofetched features therein. The low-k dielectric layer 22 may also beformed over one or more side surfaces 28 of the wafer base 24 (notshown.)

A cleaning process is performed to remove the low-k dielectric layer 22from the wafer 104, and may provide a surface 33 of the wafer that issubstantially absent low-k dielectric residue. The cleaning processdesirably removes the low-k dielectric layer 22 substantially withoutexcessively eroding or otherwise damaging the underlying wafer 104, toallow the wafer to be re-used for subsequent testing and/or processing.

In one version, a method of cleaning the wafer 104 to remove the low-kdielectric layer 22 comprises exposing a surface 30 of the dielectriclayer 22 to an oxygen-containing gas. Exposing the surface 30 to anoxygen-containing gas can oxidize the materials at the surface 30, suchas Si—C and other chemical species. The low-k dielectric layer 22 mayalso comprise pores that allow the oxygen-containing to penetrate thelayer and oxidize interior regions of the layer 22, for example, thelayer 22 may have a porosity of from about 3% to about 30% by volume,and may comprise nano-sized pores. Oxidation of the surface 30 of thelayer 22 can induce cracking and flaking of the layer 22 from thesurface 30, thus removing portions of the low-k dielectric layer 22 formthe wafer 104. A suitable oxygen-containing gas can comprise at leastone of oxygen gas, ozone and water, and in one version may desirably becomposed of oxygen gas (O₂).

In one version, the surface 30 of the dielectric layer 22 is exposed tooxygen-containing gas while heating the wafer 104 to a temperature thatis sufficiently high to oxidize the surface 30 of the layer 22. Asuitable temperature may be a temperature of at least about 700° C.,such as from about 700° C. to about 1200° C. For example, the wafer 104may be placed in a temperature controlled oven (not shown) having anoxygen-containing atmosphere with a high oxygen content, such as atleast about 50% by volume oxygen. The oven may even be continuouslypurged with an oxygen-containing gas to maintain the high oxygencontent. A suitable flow of an oxygen-containing gas into the oven, suchas O₂, may be for example from about 4000 sccm to about 10,000 sccm.

In another version, the surface 30 of the dielectric layer 22 is exposedto an energized gas comprising energized oxygen-containing species tooxidize the surface 30. Oxygen-containing gases such as O₂ can beexcited in a plasma to high energy singlet oxygen atoms that have highoxidation capability, and can also penetrate pores in the low-kdielectric layer 22 to oxidize the material. The oxygen containing gascan be energized by applying one or more of RF or microwave energy tothe gas. For example, in one version, the wafer 104 may be placed in aprocess chamber (not shown), such as a barrel plasma etcher having atleast one of electrodes, and inductor antenna, or microwave applicatorthat energize a gas to oxidize the surface 30. A suitable power level toenergize the gas may be a power level of a least about 800 Watts, suchas from about 800 Watts to about 3500 Watts, and even about 2800 Watts,for a gas pressure of from about 3 Torr to about 7 Torr. A suitable flowrate of the oxygen-containing gas in the chamber may be at least about250 sccm, such as from about 250 sccm to about 500 sccm. While thesurface 30 may be exposed to the energized gas at about 25° C., thetemperature of the wafer 104 may also be increased to improve theoxidation rate and extent. For example, the wafer 104 may be heated to atemperature of at least about 350° C., such as from about 350° C. toabout 500° C., during exposure to the energized gas.

Once the surface 30 of the low-k dielectric layer 22 has been exposed tothe oxygen-containing gas, a chemical cleaning step can be performed toremove oxidized as well as unoxidized portions of the layer 22. Thechemical cleaning step comprises immersing a surface 33 of the wafer104, such as the surface of the low-k dielectric layer 22, in a chemicalsolution having a composition that is selected to etch and remove thelayer 22, substantially without damaging or eroding underlying portionsof the wafer 104. In one version, the chemical solution comprisessilicon-removal component capable of acting on silicon-containingspecies in the dielectric layer 22, and a carbon-removal component thatis capable of acting on carbon-containing species. The silicon andcarbon-removal components operate together in the chemical solution tobreak bonds among both carbon and silicon-containing species in thedielectric layer 22, and thereby remove the low-k dielectric layer 22from the wafer 104. In one version, a suitable silicon-removal componentcomprises HF, and a suitable carbon-removal component comprises H₂SO₄.For example, the solution can comprise a mixture of from about 1% toabout 10% by weight of HF, and from about 30% to about 40% by weight ofH₂SO₄. A desired molar ratio of HF to H₂SO₄ in the solution may be fromabout 1:10 to about 1:20. While in one version the chemical solution canconsist essentially of HF and H₂SO₄, in other versions the chemicalsolution can comprise other components, such as for example at least oneof HNO₃, H₂O₂ and NH₄F. A suitable immersion time may be from about 10minutes to about 60 minutes. The chemical solution can remove a bulkportion of the dielectric layer 22, including any remaining oxidized aswell as unoxidized portions of the layer 22, and comprises a compositionthat does not excessively erode the underlying wafer 104.

Once the surface 30 has been immersed in the chemical solution to removethe low-k dielectric layer 22 from the wafer 104, a subsequent cleaningstep can be performed to etch and remove low-k dielectric residuesremaining on the wafer 104, to provide a substantially clean wafer topsurface 33, as shown for example in FIG. 1 b. In one version, thecleaning step comprises removing organic residues that remain on thewafer 104 from the dielectric layer 22, and which may not have beencompletely removed by the previous immersion in the chemical solution.An example of a cleaning step to remove remaining low-k dielectric layerresidues comprises immersing a surface 33 of the wafer 104 having low-kdielectric layer residues thereon in a solution comprising a compositionof H₂SO₄ and H₂O₂, which may be also known as a Piranha solution. Asuitable solution may comprise a concentration equivalent to, forexample, a solution formed by combining a 96% w/w solution of H₂SO₄(concentrated H₂SO₄) with a 30% w/w solution of H₂O₂, in a volumetricratio of the 98% w/w H₂SO₄ solution to the 30% w/w H₂O₂ solution of fromabout 7:3 to about 50:1, such as for example about 4:1. Thus, a suitablemolar ratio of H₂SO₄ to H₂O₂ may be from about 1.4:1 to about 31:1, suchas about 2.5:1. A temperature of the solution may be maintainedsufficiently high to promote reactions between the solution andremaining low-k dielectric layer residues to remove the residues. Forexample, the temperature may be at least about 120° C. In yet anotherversion, the surface 33 of the wafer can be exposed to an energizedoxygen-containing gas, for example in a plasma barrel etcher, to removeany low-k dielectric residues such as organic residues that remain aftercleaning with a chemical solution.

In yet a further version, the wafer 104 may be cleaned by alternatingcleaning of the wafer surface 33 with a first cleaning solutioncomprising a component that breaks Si—O bonds, and a second solutioncomprising a component that breaks Si—C bonds, to remove low-kdielectric residues from the surface. For example, the surface 33 of thewafer may be immersed in a first solution comprising at least one of HFand NH₄F, such as a solution of HF having a concentration of from about1% to about 10% weight to break Si—O bonds on the surface 33. Thesurface 33 may then be immersed in a second solution comprising H₂SO₄and H₂O₂, such as the Piranha solution, to break remaining Si—C bonds toremove remaining low-k dielectric residues. The wafer 104 may also beimmersed in the solutions in a different order, and the cleaning stepsmay be repeated until the low-k dielectric layer 22 has beensubstantially entirely removed. In general, the cleaning solutionsdesirably comprise compositions that are capable of effectively breakingbonds in the low-k dielectric material, such as Si—O, Si—CH₃ and C—Obonds, to remove the low-k dielectric layer 22 substantially withoutleaving a residue on the wafer surface 33 that could be difficult toremove and could inhibit further testing/processing of the wafer 104.

In one version, the low-k dielectric layer 22 is removed from the wafer22 by a cleaning step that involves grinding the dielectric layer 22 bya fine grinding method. A fine grinding method can be effective toremove the low-k dielectric layer 22 because the dielectric layer 22 istypically relatively structurally soft in comparison to the base 24, andthus can be removed by fine-grinding substantially without removingexcessive material from the wafer base 24. In one version of a finegrinding method, the surface 30 of the dielectric layer 22 is groundagainst an abrasive surface 32, such as an abrasive wheel 34, comprisingbonded particles of abrasive material that are capable of grinding awayand removing the low-k dielectric layer 22 from the wafer 104, as shownfor example in FIGS. 2 a and 2 b. The abrasive material can comprise,for example, particles of at least one of diamond and cubic boronnitride material, which can be bonded to the surface 32 through, forexample, a vitrified bond, resin bond or metal bond. The bondedparticles are typically sized to provide the desired low-k dielectricmaterial removal, substantially without excessively damaging orscratching the underlying wafer surface 26. For example, the bondedparticles may comprise a size of from about 1 micrometer to about 6micrometers. The abrasive material bonded to the surface 32 is capableof grinding the low-k dielectric layer 22 from the wafer 104substantially without providing a grinding slurry between the layer 22and the abrasive surface 32, which reduces the amount of clean-uprequired to refresh the wafer surface 33. The fine grinding method isalso an improvement over previous grinding methods, as the fine grindingmethod allows for grinding substantially without generating excessivesubsurface damage, as in other harsher bulk grinding methods

An embodiment of a fine grinding apparatus 36 is shown in FIGS. 2 a and2 b. This embodiment may be illustrative of an apparatus capable ofperforming a Peter Wolters fine grinding method, according to a designby Peter Wolters A. G., Rendsburg, Germany. A suitable apparatus may be,for example, Nanogrinder/4 or Multinano/3-300 commercially availablefrom Peter Wolters A. G. The apparatus 36 comprises upper and lowergrinding wheels 34 a,b, one or more of which has bonded particles ofabrasive material thereon. A plurality of wafer carriers 38 are providedthat are adapted to guide wafers 104 in a path between the wheels 34a,b. The wafer carriers 38 can be rotated to move the carriers in anorbiting circular path between the wheels 34 a,b, while rotating thewafers 104 against the abrasive surfaces 32 of one or more of the upperand lower wheels 34 a,b in a circular motion. A cooling fluid can alsobe provided between the wafers 104 and wheels 34 a,b to inhibitoverheating of the wafer 104 due to frictional forces. The grindingapparatus 36 can thus remove material from the wafer 104 to provide thedesired low-k dielectric removal results.

The fine grinding method can be used to remove a sufficient amount ofthe low-k dielectric layer 22 substantially without generating excessivesub-surface damage that could inhibit further use of the wafer 104, andwithout excessively etching or grinding away the wafer material. Thefine grinding method may be capable of removing a thickness of fromabout 1 to about 6 micrometers of material. For example, for a low-kdielectric layer 22 having a thickness of from about 0.5 micrometers toabout 4 micrometers, the fine grinding method may remove a thickness ofless than about 4 micrometers of material from the wafer 104, such asfrom about 0.5 to about 4 micrometers. Thus, the fine grinding methodmay remove a thickness of from about 50% to about 100% of the originalthickness of the low-k dielectric layer 22. Any subsurface damage thatmay be generated by the fine-grinding method is desirably low enough toallow for a subsequent polishing removal to remove any vestiges of grindmarks without requiring the removal of an excessive amount of materialfrom the wafer 104. For example, the sub-surface damage may be lowenough to be removed by polishing away a thickness of less than about 8micrometers of material from the wafer 104, which may include siliconmaterial from a silicon base 24, and desirably less than about 4micrometers of material, such as a thickness of from about 3 to about 4micrometers. Thus, the method allows for suitable preparation of thewafer surface 33 without eroding an excessive amount of material fromthe wafer.

A suitable polishing method may be, for example, a chemical mechanicalpolishing method, in which the surface 33 of the wafer 104 is rotatedagainst a polishing surface 40 of a polishing pad 42, while a chemicalslurry is provided between the pad 42 and wafer 104 to chemically andmechanically remove material from the wafer, as shown for example inFIG. 3. For example, a polishing pad comprising a Suba™ 1500 or a SPM2000, both of which are commercially available from Rodel, PhoenixAriz., U.S.A. could be provided in combination with a slurry havingabrasive particles of silica ranging in size from about 0.05 micrometersto about 0.2 micrometers in a deionized water slurry solution, such asthe Mazin® 3300 slurry commercially available from DA NanomaterialsL.L.C., Tempe Ariz., U.S.A. The chemical mechanical polishing processdesirably provides a sufficiently polished wafer 104 having a smooth andsubstantially scratch-free wafer surface 33 that is suitable forsubsequent processing and/or testing.

In one version, removal of the low-k dielectric layer 22 from the wafer104 can be achieved by polishing the wafer 104 with a polishing pad 42having a relatively high hardness. The hard polishing pad 42 takesadvantage of the relative structural softness of the low-k dielectriclayer 22, to remove the layer 22 substantially without excessivelyscratching or damaging the underlying wafer surface 26. The polishingpad can comprise a hardness of, for example, at least about 40 JIS Ahardness, such as from about 60 to about 80 JIS A hardness, and evenabout 92 JIS A hardness. The term “JIS A hardness” as used herein meansa numeric value as measured by using a durometer hardness test machineof type A as defined by JIS K 6253:1997. A suitable pad 42 having thedesired hardness may be, for example, a Rodel® MH polishing pad and mayalso be Rodel Suba™ 1200 pad, both of which are commercially availablefrom Rodel, Phoenix Ariz., U.S.A.

In the polishing process, the surface 33 of the wafer 104 is typicallyrotated against the polishing surface 40 of the high-hardness polishingpad 42, and a slurry is provided between the pad 42 and wafer 104. Asuitable slurry for polishing with the high-hardness polishing pad maybe a slurry having slurry particles comprising silica in a chemicalsolution comprising KOH, which may comprise a pH value of about 11. Thewafer 104 can be polished with the high-hardness pad 42 until asufficient amount of the low-k dielectric layer 22 has been removed,such as from about 20% to about 50% of the thickness of the low-kdielectric layer 22, and even 100% of the thickness, which may be fromabout 0.5 micrometers to about 4 micrometers of the dielectric layer 22.The relatively high hardness pad does not excessively scratch thesurface 33 of the wafer 104, and thus can provide satisfactory removalof the low-k dielectric layer 22 without damaging or excessively erodingthe underlying surface 26, as shown in FIG. 1 b. Polishing with the highhardness polishing pad 42 can thus be performed to remove substantiallythe entire dielectric layer 22 on the wafer 104, or may be performed incombination with one or more other cleaning steps. For example, thewafer 104 may be polished with the polishing pad after an initial finegrinding or other grinding process is performed to remove any remaininglow-k dielectric layer residues as well as any surface imperfectionsthat may remain on the wafer 104 after the fine grinding process. Afinal polishing process can be performed after the high hardnesspolishing step to refresh and renew the wafer surface 33, and maycomprise a light polish with a relatively soft polishing pad 42, such asa UR 100 pad commercially available from Rodel, Phoenix Ariz., U.S.A.

In one version, one or more of the cleaning steps comprising thesolutions capable of removing the low-k dielectric layer 22 are combinedwith any of the steps described above. For example, the wafer 104 may becleaned by a chemical solution before or after one or more of a finegrinding step, high hardness polishing step and oxidation step. Inanother version, one or more chemical solution cleaning steps can beperformed separately, substantially without previously heating,oxidizing or grinding the wafer 104. Suitable solutions can comprise,for example, least one of HF, NH₄F, HNO₃, H₂SO₄ and H₂O₂, wherein theconcentrations of the solution components are selected to remove theremaining dielectric layer 22 substantially without excessively etchingthe wafer 104 beneath the dielectric layer, and substantially withoutleaving low-k dielectric residues remaining on the wafer 102.Furthermore, combinations of the fine grinding, high hardness polishing,and oxidation processes may also be performed to achieve the desiredcleaning results.

In another version, a method is provided for reclaiming and refreshingwafers 104 that involves providing a removable layer 44 between thelow-k dielectric layer 22 and underlying wafer base 24, to allow easierremoval of the low-k dielectric layer 22, as shown for example in FIG.4. The removable layer 44 comprises a material that can be readilyremoved from the wafer 104 when desired, for example by etching theremovable layer 44. The removable layer 44 comprises a material that ismore easily removed than the low-k dielectric layer 22, and is alsodesirably a material that can be removed substantially without excessiveerosion of the underlying wafer base 24. The readily removable layer 44allows for the low-k dielectric layer to be “lifted-off” the wafer 104simultaneously with the removable layer 44, and thus provides for easyremoval of the low-k dielectric layer without requiring removal meansthat are specific to low-k materials.

In this version, a removable layer 44 is formed over the base 24 of thewafer 104, such as over substantially the entire underlying surface 26of the wafer 104. The removable layer 44 may be formed on the wafer 104by, for example, a deposition method, such as a chemical or physicaldeposition method, and may also be “grown” on the wafer 104, for exampleby an epitaxial layer growth method. An example of a suitable removablelayer 44 comprises a layer of silicon oxide having a thickness of fromabout 0.5 micrometers to about 2 micrometers. The wafer 104 having theremovable layer 44 formed thereon can be used for testing and/orprocessing purposes. For example, the wafer 104 can be used to testprocess results for the deposition of a low-k dielectric layer 22 on thewafer 104, and may also be used to test results for the etching of sucha low-k dielectric layer 22. The low-k dielectric layer 22 is formedover the removable layer 44, and is spaced apart from the wafer base 24by the removable layer 44, as shown in FIG. 4.

To remove the low-k dielectric layer 22, for example to refresh and/orreclaim the wafer 104, at least a portion of the removable layer 44 isimmersed in an etching solution having a composition that is capable ofetching the removable layer 44. The etching solution is preferablycapable of etching the removable layer 44 substantially without etchingthe underlying wafer base 24. The low-k dielectric layer 22 is “liftedoff” of the wafer 104 by the removal of the removable layer, and mayalso be at least partially etched and removed by the etching solution.In one version, a suitable etching solution comprises HF, and may evencomprise a buffered hydrofluoric acid solution (BHF) comprising HF andNH₄F. For example, the etching solution may comprise HF having aconcentration of from about 5% to about 49% by weight. In one version, asuitable BHF solution is a solution equivalent to a mixture of 40% byweight NH₄F and 49% by weight HF in a volumetric ratio NH₄F to HF ofabout 6:1. The removable layer 44 may be immersed in the etchingsolution for from about 0.5 minutes to about 60 minutes to remove thelayer 44. One or more post-etching steps may be performed to prepare thewafer surface 33 for subsequent testing and/or processing. For example,the surface 33 of the wafer 104 may be subjected to at least one of arinsing step and polishing step to refurbish the wafer 104. Once thewafer surface 103 has been refurbished, the removable layer 44 can bere-formed on the surface 26 of the wafer base 24 to allow furthertesting and deposition of low-k dielectric layers 22 on the wafer 22.

Additionally, the cleaning steps described above can be combined toprovide cleaning processes suitable for removing low-k dielectric layers22. For example, the removable layer 44 may be used along with one ormore of an oxidation, fine grinding and high hardness polishing processto remove the low-k dielectric layer 22. Accordingly, while preferredembodiments have been described herein, the cleaning method should notbe limited to those combinations specifically described herein.

An apparatus 102 suitable for forming the low-k dielectric layer 22 onthe wafer 104 may be a chemical vapor deposition chamber 106, anembodiment of which is shown for example in FIG. 5. The chamber 106 maybe capable of re-forming the low-k dielectric layer 22 on a wafer 104that has been cleaned, and may also be capable of depositing a low-kdielectric layer 22 on a fresh wafer 104. The chamber shown in FIG. 5comprises enclosure walls 118, which may comprise a ceiling 119,sidewalls 121, and a bottom wall 122 that enclose a process zone 113.The enclosure walls 118 can comprise a domed ceiling 119 over theprocess zone 113. A deposition gas can be introduced into the chamber106 through a gas supply 130 that includes a deposition gas source 131,and a gas distributor 132. In the version shown in FIG. 5, the gasdistributor 132 comprises one or more conduits 133 having one or moregas flow valves 134 a,b and one or more gas outlets 135 a around aperiphery of the wafer 104, as well as one or more outlets 135 b,c abovethe wafer 104 to provide an optimized flow of deposition gas in thechamber 106. An electrode 145 in an electrostatic chuck 108 of asubstrate support 100 may be powered by an electrode power supply 143 toelectrostatically hold a wafer on the support surface 180 duringprocessing. Spent process gas and process byproducts are exhausted fromthe chamber 106 through an exhaust 120 which may include an exhaustconduit 127 that receives spent process gas from the process zone 113, athrottle valve 129 to control the pressure of process gas in the chamber106, and one or more exhaust pumps 140.

In one version, the support 100 also comprises a process kit 124comprising one or more rings, such as a cover ring 126 and a collar ring128 that covers at least a portion of the upper surface of the support100 to inhibit erosion of the support 100. A lift pin assembly 154 andwafer transport 153 can also be provided to position the wafer 104 on awafer receiving surface 180 of the support 100. The lift pin assembly154 comprises a plurality of lift pins 152 adapted to contact theunderside of the wafer 104 to lift and lower the substrate 104 onto thewafer receiving surface 180. The wafer transport 153 is adapted totransport wafers 104 in and out of the process chamber 106.

In one version, the deposition gas may be energized to process the wafer104 by a gas energizer 116 comprising an antenna 117 having one or moreinductor coils 111 a,b which may have a circular symmetry about thecenter of the chamber to couple energy to the process gas in the processzone 113 of the chamber 106. For example, the antenna 117 may comprise afirst inductor coil 111 a about a top portion of the domed ceiling 119of the chamber 106, and a second inductor coil 111 b about a sideportion of the domed ceiling 119. The inductor coils may be separatelypowered by first and second RF power supplies 142 a,b. The gas energizer116 may also comprise one or more process electrodes that may be poweredto energize the process gas. A remote chamber 147 may also be providedto energize a process gas, such as a cleaning gas, in a remote zone 146.The process gas can be energized by a remote zone power supply 149, suchas a microwave power supply, and the energized gas can be delivered viaa conduit 148 having a flow valve 134 c to the chamber 106, for exampleto clean the chamber.

To process a wafer 104, for example by forming a low-k dielectric layer22 on the wafer 104, the process chamber 106 is evacuated and maintainedat a predetermined sub-atmospheric pressure. The wafer 104 is thenprovided on the support 100 by a wafer transport 153, such as forexample a robot arm, and lift pin assembly 154. The wafer 104 may beheld on the support 100 by applying a voltage to an electrode in thesupport 100 via an electrode power supply 143. The gas supply 130provides a process gas to the chamber 106 and the gas energizer 116couples RF or microwave energy to the process gas to energize the gas toprocess the wafer 104. Effluent generated during the chamber process isexhausted from the chamber 106 by the exhaust 120.

The chamber 106 can be controlled by a controller 194 that comprisesprogram code having instruction sets to operate components of thechamber 106 to process wafers 104 in the chamber 106. For example, thecontroller 194 can comprise a wafer positioning instruction set tooperate one or more of the wafer support 100 and wafer transport 153 andlift pins 152 to position a wafer in the chamber 106; a gas flow controlinstruction set to operate the gas supply 130 and flow control valves toset a flow of gas to the chamber 106; a gas pressure control instructionset to operate the exhaust 120 and throttle valve to maintain a pressurein the chamber 106; a gas energizer control instruction set to operatethe gas energizer 116 to set a gas energizing power level; a temperaturecontrol instruction set to control temperatures in the chamber 106; acleaning control instruction set to set a voltage applied to theelectrode 145 to generate an electrostatic force to press the wafer 104against the support surface 180; and a process monitoring instructionset to monitor the process in the chamber 106.

The present invention has been described with reference to certainpreferred versions thereof; however, other versions are possible. Forexample, the wafer 104 can be used in other types of applications, aswould be apparent to one of ordinary skill. Other types of cleaningsteps can also be used. Further, alternative steps equivalent to thosedescribed for the cleaning process can also be used in accordance withthe parameters of the described implementation, as would be apparent toone of ordinary skill. Therefore, the spirit and scope of the appendedclaims should not be limited to the description of the preferredversions contained herein.

1. A method of removing a low-k dielectric layer having a composition ofsilicon, oxygen and carbon from a wafer, the low-k dielectric layerhaving a k value of less than about 3, the method comprising: (a)exposing a surface of the low-k dielectric layer to an oxygen-containinggas to oxidized the surface; (b) immersing the surface in an etchingsolution comprising HF and H₂SO₄ to etch the low-k dielectric layer fromthe wafer; and (c) exposing the surface to at least one of (i) anetching solution comprising H₂SO₄ and H₂O₂, and (ii) an RF or microwaveenergized oxygen-containing gas, to remove the low-k dielectric layerfrom the wafer.
 2. A method according to claim 1 wherein (a) comprisesexposing the surface to an oxygen-containing gas that is heated to atemperature of at least about 700° C.
 3. A method according to claim 1wherein (a) comprises exposing the surface to an RF or microwaveenergized oxygen-containing gas.
 4. A method according to claim 1wherein (b) comprises immersing the surface in an etching solutioncomprising HF and H₂SO₄ in a molar ratio of from about 1:10 to about1:20.
 5. A method according to claim 1 wherein (c) comprises immersingthe surface to in an etching solution comprising H₂SO₄ and H₂O₂ in amolar ratio of from about 1.4:1 to about 31:1.
 6. A method according toclaim 1 wherein (c) comprises exposing the surface to an RF or microwaveenergized gas comprising O₂ that is energized at a power level of fromabout 800 Watts to about 3500 Watts.
 7. A method according to claim 1further comprising: (d) re-forming the low-k dielectric layer on thewafer.